Deciphering Benzene-Heterocycle Stacking Interaction Impact on the Electronic Structures and Photophysical Properties of Tetraphenylethene-Cored Foldamers  

作　　者：Zeyan Zhuang Pingchuan Shen Jianqing Li Jinshi Li Zujin Zhao Ben Zhong Tang 

机构地区：[1]State Key Laboratory of Luminescent Materials and Devices,Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates,SCUT-HKUST Joint Research Institute,South China University of Technology,Guangzhou 510640 [2]Department of Chemistry,The Hong Kong University of Science and Technology,Clear Water Bay,Kowloon,Hong Kong 999077 [3]AIE Institute,Guangzhou Development District,Huangpu,Guangzhou 510530

出　　处：《CCS Chemistry》2022年第1期286-303,共18页中国化学会会刊（英文）

基　　金：This research was made possible as a result of a generous grant from the National Natural Science Foundation of China(nos.21788102 and 21673082);the Natural Science Foundation of Guangdong Province(no.2019B030301003);the Fundamental Research Funds for the Central Universities.

摘　　要：Conjugation,as an essential chemical term used to describe electron delocalization,can be roughly grouped into two categories,through-bond conjugation(TBC)and through-space conjugation(TSC).A hybrid conjugation system integrating both TBC and TSC is rarely studied and utilized,for lack of a well-established model and difficulty of structure modification and property tuning,despite its theoretical significance and potential applications.Herein,various foldamers with a tetraphenylethene(TPE)core are employed as hybrid conjugation models to investigate structure–property correlation by introducing heterocycles of furan/thiophene into theπ-stacking TSC component.For comparison,two kinds of TPE-cored foldamers with different stacking models,a benzene–heterocycle stacking model and a benzene–benzene stacking model,are designed.Combining experimental measurements and theoretical calculations,the impact of benzene–heterocycle interaction on the hybrid conjugation natures and photophysical properties has been studied systematically.The results reveal that the benzene–heterocycle stacking model can fabricate a hybrid conjugation nature with an improved TSC component to make a more dominant contribution to the electronic transition natures than the benzene–benzene stacking model,leading to the distinguishing photophysical behavior.This work provides valuable guidance for the design of new functional materials with hybrid conjugation systems.

关 键 词：through-bond conjugation through-space conjugation aggregation-enhanced emission tetraphenylethene FOLDAMER 

分 类 号：O62[理学—有机化学]